Acid safranine dyestuffs



/N 1 i -s0. H 2 R N/ N\ Patented Jan. 19, 1937 I UNITED STATES PATENT OFFICE ACID SAFRANINE DYESTUFFS Eugen Huber and Wolfram Vogt, Leverkusen- I. G.-Werk, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application January 5, 1934, Serial No. 705,457. In Germany January 14, 1933 4 Claims. (01. 260-29) The present invention relates to new dyestuffs Our dyestuffs are further obtainable by startof the safranine series, more particularly it reing with an isorosinduline of the general formula: lates to acid safranine dyestuffs which may be represented by the probable general formula:

/N 18 17 16 5 \R, CaHa S 0311 I, J

15 15 wherein R and R. mean the same as stated above,

14 12 and condensing with an N-monosubstituted 1 p-phenylenediamine-sulfonic acid of the general formula: wherein y stands for aryl, aralkyl, alkyl or hydro- 29 aryl, such as phenyl, substituted phenyl, benzyl, /N- NH,

substituted benzyl, methyl, ethyl, cyclohexyl, R y I and R stand for alkyl, aralkyl or aryl, such as 1 sosn methyl, ethyl, benzyl phenyl, which radicals may wherein y means the same as stated above, 1n bear substltuents, and wherein the nucle1 may be the presence of an oxidizing agent.

further substituted, for example, by alkyl, alkoxy, The dyestuffs thus obtainable are in form of the carboxylic aciqgroup the sulfonic acid group their alkali metal salts generally dark, waterfi i gt q s gs' re obt inabl b st fin soluble powders, dyeing the fibre generally clear Y a 9 y 1 g blue to greenish-blue shades of good fastness with an isorosmduline-fi-sulfomc acid of the genproperties 30 eral formula: v The invention is illustrated by the following examples, without being limited thereto:

Example 1.-The isorosinduline-l.6.13-trisulfonic acid, prepared in the usual manner from 32 grams of the sodium salt of -sulfophenylep- R naphthylamine and 26.5 grams of the sodium salt of 4-a-minodiethylaniline-3 sulfonic acid, is heated with 28 grams of the sodium salt of 4- aminodiphenylamine-2-sulfonic acid in an aqueous solution with the addition of 20 grams of crystallized sodium acetate. The dyestufi thus obtained corresponding to the probable formula:

wherein R and R mean the same as stated above and which may bear further substituents in the nuclei, and condensing with an N-monosubstituted p-phenylenediamine-sulfonic acid of the general formula: soin HNO-N moon),

wherein 1/ means the same as stated above, the process being more fully described inthe following examples.

OCHa SOaH is soluble in concentrated sulfuric acid with grassgreen, in hot water with a clear blue coloration and dyes wool clear blue shades of good fastness to light, washing and fulling.

Emample 3.The isorosinduline-1.6-disulfonic acid, prepared in the usual manner from grams of 2.5-dichlorophenyl -,B- naphthylamine and 26 grams of 4-aminodiethylaniline-3-sodium sulfonate, is caused to react with 2'-methoxy-4- aminodiphenylamine-2-sulfonic acid in aqueous solution as described in Example 1. The dyestuif obtained having in the free state probably the following formula:

is soluble in concentrated sulfuric acid with a grass-green, in water with a clear greenish-blue coloration. It dyes wool clear greenish-blue even shades fast to light and washing.

The dyestuff having in the free state the following formula:

SOaH

prepared in an analogous manner exerts similar properties.

Example 4.- gram-molecular proportion of the 11-methyl-diethylisorosinduline-1.6-disu1- fonic acid, prepared in the usual manner, is

heated in aqueous solution with the addition of sodium acetate with gram-molecular proportion of 4-aminomonomethylaniline-2sulfonic acid. The dyestufif obtained corresponding in the free state to the following formula:

SOaH

is soluble in concentrated sulfuric acid with a grass-green, in water with a clear blue coloration. It dyes wool clear blue shades of good properties, and compared with the corresponding dyestuif containing the 4-aminodimethylaniline-Z-sulfonic acid radical in the 6-position it is distinguished by a highly improved fastness to alkalies.

Example 5.In an analogous manner as described in Example 4 the same isorosindulinesulfonic acid is condensed with 4-aminobenzylaniline-Z-sulfonic acid, yielding a dyestuff having in the free state the probable formula:

It is soluble in concentrated sulfuric acid with a green, in water with a clear blue coloration and dyes wool clear blue shades. Compared with the corresponding dyestuff containing in the 6-position the radical of 4-aminoethylbenzylaniline-Z-sulfonic acid it is distinguished by a remarkable improvement of the fastness to alkalies.

Example 6.-The dyestuff having in the free state the probable following formula:

prepared analogously to the process described in Example 4 with the aid of l-aminocyclohexylaniline-2-sulfonic acid, exerts properties similar to those ofthe dyestuffs prepared according to Example 5. j

Example 7.The isorosinduline-1.6-disu1fonic acid, prepared in the usual manner from 23.5 grams of a-tolyl-p-naphthylamine and 23.8 grams of 4-aminodimethylamine-3-sodiumsulfonate, is heated in aqueous solution or aqueous alcoholic solution with 4 methoxy-4-aminodiphenylamine- 2-su1fonic acid as described in Example 1. The dyestufi obtained corresponding in the free state to the probable formula:

is soluble in concentrated sulfuric acid with a grass-green, in hot water with a blue coloration and dyes W001 clear blue shades of good fastness properties.

Example 8.In an analogous manner as described in Example 7 there is prepared a dyestufir having in the free state the following formula:

H 02H: HW ILQM N N 03H I and having similar properties as the dyestuff prepared in accordance with Example 7.

Example 9.The isorosinduline, prepared in the usual manner from nitrosoethylbenzylaniline-sulfonic acid and phenyl-fl-naphthylamine,R

istransformed in the usual manner into the 6- sulfonic acid by the action of sodium bisulfite;

this sulfonic acid is then condensed with 4- aminodiphenylamine-Z-sulfonic acid to the safranine of the probable formula:

The dyestuff is soluble in concentrated sulfuric acid with a green, in water with a blue coloration and dyes wool reddish-blue shades.

Example 10.--The dyestuff having in the free state the following formula:

being obtained according to the process described in Example 1, has properties similar to those of the dyestuif prepared in accordance with Example 7.

Example 11.--The dyestufi having in the free state the following formula:

Cz r-OH SOJI being obtained according to the process described in Example 1, has properties similar to those of the dyestuff prepared in accordance with Example 7.

Example 12.The dyestuif having in the free state the following formula:

N aCz\ n 2 s N so; l I V w.

SOaH

SOzH

being obtained according to theprocess described in Example 1, dyes Wool greenish-blue shades of good fastness properties.

Example 13. The'dyestufi having in the free state the following formula:

being obtained according to the process described in Example 1, dyes wool greenish-blue shades of good fastness properties.

Example 14.The isorosinduline-sulfonic acid of the formula:

is stirred in aqueous pyridine of 50% strength with 2'-methoxy-4-aminodiphenylamine-2-sulfonic acid and with the addition of nitrobenzene as oxidizing agent and of caustic soda, until a test portion dissolves in concentrated sulfuric acid with a clear green coloration. The dy'estufi thus obtained is identical with that described in Example 2.

We claim:

1. Dyestufis of the safranine series selected from the group of compounds consisting of dyestufis of the formula ing the fibers generally clear blue to greenish blue shades of good fastness properties.

2. Dyestuffs of the safranine series as defined in claim 1 in which R and R stand for lower alkyl radicals.

3. Dyestuffs of the safranine series as defined in claim 1 in which R and R stand for an ethyl radical.

4. The dyestuff having in the free state the following formula:

OOHg SOsH being soluble in concentrated sulfuric acid with grass-green, in hot water with a clear blue coloration and dyeing wool clear blue shades fast to light, washing and fulling.

EUGEN HUBER. WOLFRAM VOGT. 

